DE2531342A1 - Washing textiles and dishes - using compsns. contg. calcium bonding crystalline aluminium silicates having rounded corners and edges - Google Patents

Abstract

Solid surfaces are washed and cleaned by using an aq. bath contg. finely divided dispersed water-insol. synthetic crystalline Al silicates having compsn. 0.7-1.1 Cat2/n.1 Al2O3.1.3-3.3 SiO2 (I) (where Cat is a Ca ion-exchangeable cation having valency n, esp. an alkali cation, partic. Na), as bonding agents for water-hardeners. Novelty consists of using (I) having rounded corners and edges (cpds.I'). Pref. >=80% (I') have particle size 8-0.01 (6-0.01)u, and (I') contain no particles >30mu. Use of (I'), in place of well-formed crystals of (I), accelerates ion exchange and improves washing power. (I') form a more stable suspension in treatment baths and are rinsed out more easily from machinery and articles. Use of (I') allows lowering P content of baths to 0.6 (0.3) g/l organic and/or inorganically bonded P. In an example, (I') contg. 0.99 Na2O. 1 Al2O3. 1.83 SiO2 4H2O was tested by washing cotton at 90 degrees C, without other additives. Washing power corresponded to that of Na5P3O10.

Description

"Process for ash and cleaning the surfaces of solid materials, in particular of textiles "The current detergents or cleaning agents contain often larger amounts of condensed phosphates, especially triphosphate, the are responsible for the good cleaning effect of these agents. The phosphate content These funds are used by the general public in connection with environmental protection issues criticized; it is often of the opinion that this is about the water in Rivers and lakes use phosphate for the eutrophication of water, i.e. to a Increase in algae growth and oxygen consumption. One is therefore endeavors to remove the phosphate from washing and cleaning processes or from the ones used for them To remove funds or to substantially reduce its share.

In the German Offenlegungsschrift 2 412 837 (D 4642 / 4787/4819) describes a method for washing textiles, in which these with a Fleet loading.

acts are, in the finely divided water-insoluble, a calcium binding capacity of at least 50 mg CaO / g of anhydrous active substance (= AS), if appropriate Compounds of the general formula containing bound water (Cat2 / nO) x . Me2O3. (SiO2) y in the catalyst is a calcium-exchangeable cation of valency n, x is a number from 0.7 - 1.5, Me Boron or Aluminum wid y is a number from o, 8 - 6, are preferably from 1.3 to 4, are suspended.

These water-insoluble, finely divided silicates can be X-ray amorphous or be crystalline. You can use phosphates instead of phosphates, in particular, when washing fabrics of the triphosphate. Crystalline aluminum silicates are preferably used the composition: 0.7 - 1.1 Na2O. A1203. 1.3-2.4 5102.

Also aluminum silicates with the composition 0.7 - 1.1 Na2O. Al2O3 . > 2.4 -3.3 SiO2 are according to the German. Disclosure of particular practical interest. These types of aluminum silicate are produced synthetically; they have an active substance in the range of 100-200 mg CaO / g anhydrous Calcium binding capacity, but they differ in their crystal structures.

The water-insoluble, cation-exchanging substance is used as the active substance Silicate of the above definition denotes the bound water of which by one-hour Heating to 800 ° C was removed.

The above derinated aluminum silicates can be easily removed produce, preferably by mixing aqueous silicate and aluminate solutions. During the precipitation process it is advantageous to stir the suspension vigorously, whereby the formation of small particle sizes is promoted. Even with a subsequent During the crystallization process, it is advisable to stir the crystallizing mass. Man A product can thus be obtained which consists of at least 80% by weight particles of one size between 10 and 0.01μ, in particular between 8 and 0.1μ, and practically none Contains Pratikeln> 40 µ.

The cation-exchanging water-insoluble silicates defined above, In particular, the aluminum silicates, according to the teaching of the cited priority Patent applications in the aqueous treatment liquors with advantage together with one Addition of a water-soluble complexing or precipitating agent for calcium ions as well as, if necessary, together with other common components of detergents and cleaning liquors such as surfactants, bleaches, dirt carriers, etc. are used.

The invention relates to a method for washing and cleaning solid materials, especially for washing and bleaching textiles and for machine cleaning of dishes, with an aqueous liquor, in the finely divided water-insoluble, capable of binding the hardness components of water and a calcium binding capacity Water containing 100 - 200 mg CaO / g anhydrous active substance, possibly bound water containing, synthetic. Manufactured crystalline aluminum silicates of the composition 0.7 - 1.2 Cat2 / NO. 1.0 Al2O3. 1.3 - 3.3 SiO2, in the cat one with the calcium ion exchangeable cation of valence n, preferably an alkaline cation and in particular the sodium cation means, are suspended, characterized in that these Aluminum silicate crystallites have rounded corners and edges. Preferably consist of at least 8o% of these crystallites with rounded corners and edges from particles with a size of 8 - 0.01, u, especially 6 - and have practical no particles larger than 30 ji. The mean particle diameter of these crystallites is mostly in the range of 3 - 6ji.

Surprisingly, in the use according to the invention, the Aluminum silicate crystallites with rounded corners and edges observed that this in comparison to the aluminum silicates with well-developed crystal forms the same Composition and practically the same calcium binding capacity a faster process the ion exchange and an improvement in washing power. Also educate the crystalline aluminum silicates with rounded corners and edges a comparatively more stable suspension in the treatment fiot and thus also lead to an improved Can be rinsed out of washing machines, dishwashers and textile fabrics or can be rinsed off from hard surfaces.

Preferably produced and used aluminum silicate crystallites with rounded corners and edges, the sodium aluminum silicates are those given above Composition because of the economically favorable production method from light accessible raw materials.

If you want the aluminum silicates used according to the invention with rounded To produce corners and edges, one starts with one approach with Vortcil, its molar composition preferably in the range 2.5-6.0 Kat2 / nO; 1.0 A1203; 0> 5 - 5.0 SiO2; 60-200 1120, where Kat2 / n has the meaning given above and in particular that denotes sodium ion. This approach is used in the usual way Brought crystallization. This is advantageously done by the Approach at least 1/2 hour at 70-120 ° C, preferably at 80-95 ° C tester Stir heated. The crystalline product is made in a simple manner isolated by separating the liquid phase. It may be advisable to Rinse and dry the products with serum before further processing.

Even when working with an approach that has little composition deviates from the above, products with rounded corners are still obtained and edges, especially if the deviation relates only to one of the above refers to four concentration parameters. However, the farther it is from the above Preparation conditions removed, the less the rough edges of the products of the process rounded) or

one obtains products that have only a few cation-exchanging properties own.

The approach with the above composition is preferred obtained by mixing an alkali silicate solution with an alkali aluminate solution or an alkali silicate, an alkali aluminate and an alkali hydroxide solution. It is of secondary importance which mixing direction is followed , i.e. which of the solutions to be mixed is presented and which are added will. For the formation of crystallites with rounded corners and edges primarily the concentration ratios in the mixture of these solutions due to a certain alkali content and a certain water content, of importance. Accordingly, it can be said that from the crystal nuclei in the gel of the mixture under the influence of the higher alkali content and the higher total concentration to ion compared to the manufacturing conditions for aluminum lilcate with pronounced Crystal forms the formation of the crystallites used according to the invention with rounded ones Corners and edges complete, being under crystallites with rounded corners and Edges all shapes with truncated corners tuid edges up to almost spherical Be understood For the formation of small particle sizes the approach conditions explained above already contribute in the same direction wixkt intensive stirring during the precipitation process, which makes the with each other mixed aluminate and silicate solutions - which also enter the reaction vessel at the same time can be conducted - subject to strong shear forces. Even during the subsequent Crystallization at elevated temperature can be achieved by stirring the crystallizing mass be beneficial.

Nevertheless, undesired agglomeration of crystallite particles can occur during drying occur, so that it is advisable to use these secondary particles in a suitable manner, e.g. by air separation. Aluminum silicates that occur even in a coarser condition, which have been ground to the desired grain size can be used. For this are suitable e.g.

Mills and / odex air classifiers or their combinations. The latter are for example in Ullmann: "Enzyklopadie der technischen Chemie" Volume 1, 1951, pages 632-634.

The necessary to achieve a good washing or cleaning effect The amount of aluminum silicate depends on the one hand on its calcium binding capacity, on the other hand on the amount and degree of soiling of the materials to be treated and of the hardness and the amount of water used. When using hard water it is advisable to measure the amount of aluminum silicate so that the residual hardness of the water no more than 5 ° dH (corresponding to 50 mg CaO / l), preferably 0.5-2 ° dH (5-20 mg CaO / l). To achieve an optimal washing or cleaning effect it is recommended, especially with heavily soiled substrates, a certain amount To use excess aluminum silicates in order to also reduce the impurities in the detached to bind all or part of the tIärtebildern contained. Accordingly, the application concentration of the aluminum silicates in the range of preferably 0.2-10 g AS / l, in particular 1 - 6 g of Asil lie.

It is also advantageous if you add a substance to the treatment liquor adds a complexing agent to the calcium present in the water as a hard builder and / or has a precipitating effect, since the impurities then move much faster and / or have it removed completely. As complexing agents for calcium are for the purposes of the invention also include substances with such a low complexing capacity suitable that they have not been regarded as typical complexing agents for calcium so far has, however, such compounds often have the ability to cause the precipitation of To delay calcium carbonate from aqueous solutions.

The beneficial effect of this complex-forming resp.

precipitating substances is already possible with small added amounts of e.g. 0.05 - 2 g / l, especially 0.1 - 1 g / l can be determined. Also much larger quantities can be used, but when using phosphorus-containing complexing agents or precipitants choose such amounts that the phosphorus pollution of the wastewater is significantly lower than when using the currently usual preparations based on Ti1i phosphate.

The complexing or precipitating agents include inorganic ones Nature, such as pyrophosphate, triphosphate, higher polyphosphates and metaphosphates.

Organic compounds used as complexing or precipitating agents serve for calcium, can be found under the porycarboxylic acids, hydroxycarboxylic acids, Aminocarboxylic acids, carboxyalkyl ethers, polyanionic polymers, especially the polymeric carboxylic acids and phosphonic acids, these compounds mostly in Form of their water-soluble salts are used.

Examples of polycarboxylic acids are general dicarboxylic acids Formula HOOC- (CH2) n-COOH with n = 0 - 8, also maleic acid, methylenemalonic acid, Citraconic, mesaconic, itaconic, non-cyclic polycarboxylic acids with at least 3 carboxyl ..

groups in the molecule, such as tricarballylic acid, aconitic acid, ethylene tetracarboxylic acid, 1,1,3,3-propane-tetracarboxylic acid, 1,1,3,3,5,5-pentane-hexacarboxylic acid, hexane-hexacarboxylic acid, cyclic di- or polycarboxylic acids, such as cyclopentane-tetracarboxylic acid, cyclohexane-hexacarboxylic acid, Tetrahydrofuran tetracarboxylic acid, phthalic acid, terephthalic acid, benzene tri-, -tetra- or pentacarboxylic acid and mellitic acid.

Examples of hydroxymono- or polycarboxylic acids are glycolic acid, Lactic acid, malic acid, tartronic acid, methyltartronic acid, gluconic acid, glyceric acid, Citric acid, tartaric acid, salicylic acid.

Examples of aminocarboxylic acids are glycine, glycylglycine, alanine, Asparagine, glutamic acid, aminobenzoic acid, iminodi- or triacetic acid, hydroxylethyl-iminodiacetic acid, Ethylenediamine-tetraacetic acid, hydroxylethyl-ethylenediamine-triacetic acid, diethylenetraimine-pentaacetic acid as well as higher homologues obtained by polymerizing an N-aziridylcarboxylic acid derivative, e.g. acetic acid, succinic acid, tricarballylic acid, and subsequent saponification, or by condensation of polyamines with a molecular weight of 500 to 10 000 can be produced with chloroacetic acid or bromoacetic acid salts.

Examples of carboxyallryl ethers are 2,2-oxydisuccinic acid and other ether polycarboxylic acids, especially those containing carboxymethyl ether groups Polycarboxylic acids, including corresponding derivatives of the following polyvalent alcoholes or hydroxycarboxylic acids that include wholly or partially with the glycolic acid can be etherified: glycol, di- or triglycols, glycerine, di- or triglycerols, Glycerol monomethyl ether, 2,2-dihydroxymethylpropanol, 1,1,1-trihydroxymethyl-ethane, 1,1,1-trihydroxymethylpropane, erythritol, pentaerythritol, glycolic acid, lactic acid, Tartronic acid, methyl tartronic acid, glyceric acid, erythronic acid, malic acid, citric acid, Tartaric acid, trihydroxyglutaric acid, saccharic acid, mucic acid.

The carboxymethyl ethers are the transition types to the polymeric carboxylic acids to name the sugar, the starch and the cellulose.

Among the polymeric carboxylic acids, for example, the polymeridates of Acrylic acid, hydroxyacrylic acid, maleic acid, itaconic acid, mesaconic acid, aconitic acid, Methylenemalonic acid, citraconic acid and the like, the copolymers of the above Carboxylic acids with one another or with ethylenically unsaturated compounds such as ethylene, Propylene, isobutylene, vinyl alcohol, vinyl methyl ether, furan, acrolein, vinyl acetate, Acrylamide, acrylonitrile, methacrylic acid, crotonic acid etc., e.g.

the 1: 1 copolymers of maleic anhydride and ethylene or Propylene and furan play a special role.

Further polymeric carboxylic acids of the polyhydroxypolycarboxylic acid type or polyaldehyde-polycarboxylic acids are essentially composed of acrylic acid and acrolein units respectively.

Acrylic acid and vinyl alcohol units built up substances through Copolymerization of acrylic acid and acrolein or -by polymerization of acrolein and subsequent Cannizzaro reaction, optionally in the presence of formaldehyde are available.

Examples of organic phosphorus formers are alkane polyphosphonic acids, Amino and hydroxyalkane polyphosphonic acids and phosphonocarboxylic acids such as the Compounds methanediphosphonic acid, propane-1,2,3-triphosphonic acid, butane-1,2,3,4-tetraphosphonic acid, Polyvinylphosphonic acid, 1-aminoethane-1,1-diphosphonic acid, 1-amino-1-phenyl-1,1-diphosphonic acid, Aminotrimethylene triphosphanic acid, methylamino- or ethylaminodimethylene diphosphonic acid, Ethylene diaminotetramethylene tetraphosphonic acid, 1-hydroxyethane-1,1-diphosphonic acid, Phosphonoacetic acid, phosphonopropionic acid, 1-phosphonoethane-1,2-dicarboxylic acid, 2-phosphonopropane-2,3-dicarboxylic acid, 2-phosphonobutane-1,2,4-tricarboxylic acid, 2-phosphonobutane-2,3,4-tricarboxylic acid and copolymers of vinylphosphonic acid and acrylic acid.

The inventive use of the aluminum silicates described above it is - even when using phosphorus-containing inorganic or organic complexing- respectively.

Precipitant for calcium - easily possible the phosphorus content the treatment liquors to a maximum of 0.6 g / l, preferably to a maximum of 0.3 g / l to keep organically and / or inorganically bound phosphorus. But it can work completely phosphorus-free even with good success.

The one working according to the invention, using aluminum silicates Process can be found in numerous areas of technology and household for the use various cleaning tasks. Examples of such areas of application are the cleaning of Gerafvell, equipment, pipes and vessels made of wood, Plastic, metal, ceramics, glass etc. in industry or in commercial operations, the cleaning of furniture, walls, floors, objects made of ceramics, glass, metal, Wood, plastic, cleaning polished or painted surfaces in the household etc. Particularly important areas of application are washing and bleaching of textiles and the machine cleaning of all kinds of dishes in industry Laundries and in the household.

The textiles to be washed can be made from a wide variety of fibers of natural or synthetic origin.

These include, for example, cotton, regenerated cellulose or linen as well as textiles, the highly crinkled cotton or synthetic man-made fibers, such as e.g. polyamide, polyester, polyacrylonitrile, polyurethane, polyvinyl chloride or polyvinylidene chloride fibers contain. The detergents according to the invention can also be used for washing the as "Easy-care", sometimes also called "non-iron" textiles made from synthetic fiber / cotton blended fabrics use.

When washing and cleaning the mentioned textiles using aqueous cleaning liquors containing the aluminum silicates in suspension the washing or cleaning effect is achieved through the usual constituents of such treatment liquors to enhance. These include, for example: surfactants, surfactant-like or non-tensile Id-like foam stabilizers or inhibitors, textile softeners, neutral or alkaline reacting builder substances, chemically acting bleaching agents, solc stabilizers and / or activators for these, dirt carriers, corrosion inhibitors, antimicrobial Substances, enzymes, brighteners, dyes and fragrances, etc.

When using one or more of the above, In ltasch and Cleaning liquors for textiles Commonly present substances are expedient the following concentrations are observed: o, i - 2.5 g / l surfactants, 0.5 - 6 g / l builder substances, 0.15 - 0.4 g / l active oxygen or equivalent amounts of active chlorine.

The pII-llert of the textile treatment liquors can depending on the washing or cleaning substrate in the range of 6-13, preferably 8.5-12.

All dishes are in the household, in commercial establishments and in the Industric when storing, preparing and serving food and beverages and equipment to be cleaned after use Ceramic means material, glass, plastic, wood and metal.

The method according to the invention can therefore except in the liaushalt and in Catering and accommodation industry also in large kitchens, dairies, in the beverage industry, such as breweries, in lemonade, mineral water and fruit juices manufacturing or processing companies for machine washing and cleaning, especially bottles. The method is also suitable for Rinsing of laboratory equipment, even if this is caused by residues other than food are contaminated.

In the case of machine washing of dishes, those defined above are used Aluminum silicates are preferably used in a concentration of 0.5-3 g / l. In particular if you combine them with alkaline reacting substances in such an amount be used so that the pH of the treatment liquor is in the range of 8-13. Such alkaline reacting substances are preferably alkali silicates and alkali carbonates, and - if higher pH values are sought - caustic alkalis.

The effect of the dishwashing process according to the invention or

the means used for its implementation can be determined by adding small amounts of surfactants, especially nonionic surfactants, improve. In addition, the addition of oxidizing substances, in particular active chlorine compounds, possibly also of per compounds, proven to be advantageous.

Nan has been looking for a useful phosphate substitute for quite some time, that is not only able to bind calcium, but also biologically in the wastewater can be reduced. A wide variety of organic compounds are therefore used as phosphate substitutes suggested. The technical teaching according to the invention, for this purpose water-insoluble, Using cation-exchanging aluminum silicates is therefore a complete departure from the direction of work of the entire professional world. It is particularly surprising that the water-insoluble Alur.winiumsilikate for example from textiles completely be flushed out.

The use of aluminum silicates has two effects Relief of the wastewater: The amount of phosphorus that gets into the wastewater becomes closer greatly reduced or eliminated entirely; in addition, the aluminum silicates do not require any Oxygen for biodegradation. They are piincral in nature, sit down in sewage treatment plants or in natural waters gradually and thus meet the Idcal requirements for a phosphate substitute.

But also in terms of washing and cleaning technology, they have already proposed phosphate substitutes Advantages: They adsorb colored ones Impurities, support the graying inhibition and thus save chemically acting bleaching agent The invention further relates to the implementation of the claimed process certain agents that contain calcium-binding substances. These are characterized in that they wash and bleach in addition to at least one or inorganic or organic compound with a cleaning effect as calcium binding compound contain the aluminum silicates defined above. Furthermore Other usual, mostly present in smaller amounts, can be used in such agents Auxiliaries and additives must be present.

The aluminum silicate content of such agents can be in the range of 5 - 95, preferably 10 - 60%.

The agents according to the invention can furthermore contain complexing agents or Contain precipitants for calcium, their action, depending on the chemical nature of the mean, can already be seen at levels of 2-15 f. These complexing agents respectively.

Precipitants can also be contained in larger quantities in the preparations be, but with the restriction that then the amount of in the invention Means optionally present inorganic phosphates and / or organic Phosphonate is not greater than a calculated total phosphorus content of the agent of 6, preferably 3%.

All of these percentages are percentages by weight; they refer to each other in the case of aluminum silicates, the dried water that is still bound Substance.

To the washing, bleaching or cleaning effect, in the washing or cleaning agents include, for example, surfactants, surfactant-like or non-surfactant foam stabilizers or inhibitors, fabric softeners, neutral or alkaline reacting structural substances, chemically acting bleaching agents and stabilizers and / or activators for these. Others, mostly less I: cngc present auxiliaries and additives are e.g. corrosion inhibitors, antimicrobial Substances, dirt carriers, enzymes, brighteners, dyes and fragrances, etc.

The composition more typical, at temperatures in the range of 50 - 500 OC laundry detergent to be used is in the range of the following recipe: 5 - 30 t of anionic and / or nonionic and / or zwitterionic surfactants, 5 - 70 % Aluminum silicates as defined above, 2 - 45% complexing agents for calcium, 0 - 50% washing alkalis not capable of complex formation (= alkaline structural substances) O - 50 A bleaching agents and others, mostly in smaller quantities in laundry detergents existing additives.

The composition of typical machine wash detergents lies in the Under the following recipe: 10 - 60% alkali silicates and / or carbonates and / or -hydroxides, which are partly due to preferably inorganic phosphorus-containing complexing agents, in amounts that correspond to the maximum amounts for phosphorus specified above, can be replaced, 10 - 65 ç aluminum silicates of the above definition, 0 - 40 ffi other common ingredients of dishwasher detergents.

To the other common ingredients of machine dishwashing detergents include the following substances, preferably at least one of which is in the specified amounts present 1.0 - 10% active chlorine containing active oxygen Substances, 0.5-10% surfactants, especially non-ionic surfactants, 2.0-20% sodium sulfate and / or water.

There now follows an enumeration of those for use in the inventive Agents suitable substances.

The surfactants contain at least one hydrophobic organic in the molecule Remainder and a water-solubilizing anionic, zwitterionic or nonionic Group. The hydrophobic radical is usually an aliphatic hydrocarbon radical with 8-26, preferably 10, 22 and in particular 12-18 carbon atoms or around one alkyl aromatic radical with 6-18, preferably 8-16, aliphatic carbon atoms.

As anionic surfactants, e.g. soaps made from natural or synthetic, preferably saturated fatty acids, possibly also from resin or naphthenic acids usable .. Suitable synthetic anionic surfactants are those of the sulfonate type, Sulfates and the synthetic carboxylates.

As surfactants of the sulfonate type, there are alkylbenzene sulfonates (C9-15-alkyl), Mixtures of alkene and I-Iydr oxyalliansul fona th and disulfonates, such as. man for example, from monoolefins with a terminal or internal double bond Sulphonation with gaseous sulfur trioxide and subsequent alkaline or acidic Llydrolysis of the sulfonation products obtained into consideration. Alkanesulfonates are also suitable, that from alkanes by sulfochlorination or sulfoxidation and subsequent hydrolysis or Ncuralisaticn or are obtainable by bisulfite addition to olefins. Further useful sulfonate type surfactants are the esters of α-sulfo fatty acids, e.g. the α-sulfonic acids from hydrogenated methyl or ethyl esters of coconut, palm kernel or tallow fatty acid.

Suitable surfactants of the sulfate type are the primary sulfuric acid monoesters Alcohols (e.g. from coconut fatty alcohols, tallow fatty alcohols or oleyl alcohol) and those of secondary alcohols. Also suitable are - sulfated fatty acid alkanolamides, Fatty acid monoglycerides or reaction products of 1 - 4 mol of ethylene oxide with primary or secondary fatty alcohols or alkyl phenols.

Other suitable anionic surfactants are the fatty acid esters or -amides of hydroxyl or amino carboxylic acids or sulonic acids, such as the fatty acid sarcosides, -glycolates, -lactates, -taurides or -isethionates.

The anionic surfactants can be in the form of their sodium, potassium and Ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine are present.

Addition products from 4 to 40 are preferred as nonionic surfactants 4 - 20 moles of ethylene oxide in 1 mole of fatty alcohol, alkylphenol, fatty acid, fatty amine, fatty acid amide or alkanesulfonamide can be used. The addition products are particularly important from 5 - 16 mol of ethylene oxide to coconut or tallow fatty alcohols, to oleyl alcohol or to selective alcohols with 8 - 18> preferably 12 - 18 carbon atoms, as well as to mono- or dialkylphenols with 6-14 carbon atoms in the alkyl radicals. In addition to these water-soluble However, nonionics are also not or not completely water-soluble polyglycol ethers with 1 - 4 ethylene glycol ether residues in the molecule of interest, especially if used together with water-soluble nonionic or anionic surfactants will.

Furthermore, the water-soluble, 20 - Containing 250 ethylene glycol ether groups and 10-100 propylene glycol ether groups Addition products of ethylene oxide with polypropylene glycol (= Pluronics R), alkylenediamine-polypropylene glycol (= Tetronics R) and alkyl polypropylene glycols with 1 - 10 carbon atoms in the alkyl chain useful in which the polypropylene glycol chain acts as a hydrophobic residue.

There are also nonionic surfactants of the amine oxide or sulfoxide type usable.

The foaming power of the surfactants can be determined by a combination of suitable Increase or decrease types of surfactants; a reduction can also be achieved Achieve additions of non-surfactant organic substances.

Suitable foam stabilizers are, above all, sulfonate surfactants - or sulfate type, capillary-active carboxy- or sulfobetaines as well as those mentioned above Alkylolamide type nonionics; in addition, fatty alcohols or are for this purpose higher terminal diols have been proposed.

A reduced foaming power, which is desirable when working in machines is often achieved by combining different types of surfactants, e.g. from Sulphates and / or sulphonates with nonionics and / or with soaps. In the case of soaps, increases the foam damping with the degree of saturation and the carbon number of the fatty acid residue; So soaps made from saturated C20-24 fatty acids are particularly suitable as anti-foam agents.

The non-surfactant foam inhibitors may include Chlorine-containing N-alkylated aminotriazines, which can be obtained by reacting 1 mol Cyanuric chloride with 2-3 mol of a mono- and / or diakylamine with 6-20, preferably 8 - 18 carbon atoms in the alkyl radical. Propoxylated and / or butoxylated drugs have a similar effect Aminotriazines, e.g. Products obtained by adding 5 - 10 @ moles of propylene oxide 1 mol of melamine and further addition of 10-50 mol of butylene oxide to this propylene oxide derivative receives.

Water-insoluble foam inhibitors are also suitable as non-surfactant-like foam inhibitors organic compounds such as paraffins or haloparaffins with melting points below from 100 OC, aliphatic C18- to Cl; O-ketones as well as aliphatic carboxylic acid esters, those in the acid or alcohol radical, optionally also in each of these two radicals, contain at least 18 carbon atoms (e.g. triglycerides or fatty acid fatty alcohol esters); they can be used especially with combinations of surfactants of the sulfate and / or sulfonate type use with soaps to steam the foam.

Particularly low-foaming nonionics that both alone.

as well as in combination with anionic, zwitterionic and nonionic Surfactants can be used and the foaming power of highly foaming surfactants reduce, are the addition products of propylene oxide to those already mentioned capillary-active polyethylene glycol ethers as well as those already described Addition products of ethylene oxide with polypropylene glycols and with alkylenediamine polypropylene glycols or on C-10 alkyl polypropylene glycols.

alkaline reacting inorganic or organic salts.

Usable salts are, for example, the bicarbonates, carbonates, borates or silicates of alkalis, alkali sulfates and the alkali salts of organic, sulfonic acids, carboxylic acids and non-capillary-active, 2 - 9 carbon atoms Sulfocarboxylic acids. These include, for example, the water-soluble salts of benzene, Toluene, xylene or cumene sulphonic acid and of suffoacetic acid, sulphosuccinic acid or sulfophthalic acid.

Those mentioned at the beginning as complexing agents or precipitants for calcium Compounds are all useful as builders; you can therefore in the Agents according to the invention may also be present in larger quantities than is necessary to fulfill their function as complexing agents or precipitants for calcium is necessary.

The components of the preferably used as laundry detergents or as household cleaning agents The products to be added, in particular the scaffold substances, are usually selected in such a way that that the preparations react neutrally to strongly alkaline, so that the pH value a @% solution of the preparation is usually in the range of 7-12. E.g. Fine detergents mostly neutral to slightly alkaline reaction (pH value = 7 - 9.5), while soaking, prewash and heavy duty detergents are more alkaline (pH value = 9.5 - 12, preferably 10 - 11.5) set ind.

If higher pI values are required for special cleaning purposes, see above these can be achieved by using alkali silicates with suitable Na2O: SiO2 ratios or easily adjusted from caustic alkalis.

Among the compounds that serve as bleaching agents and yield H2O2 in water have sodium perborate tetrahydrate (NaBO2. H2O2. 3 H2O) and monohydrate (NaBO2. H2O2) special meaning. However, there are also other borates which produce H 2 O 2 usable, e.g. the Perborax Na2B4O7 4 H202. These connections can be partial or completely through other active oxygen releasers, in particular through - peroxyhydrates, -like peroxycarbonates (Na2CO) t 1.5 H2O2), peroxypyrophosphates, citrate perhydrates, Urea-H2O2 or melamine-H2O2 compounds as well as peracid that supplies H2O2 Salts, e.g.

Caroate (KNSO5), perbenzoate or peroxyphthalate can be replaced.

It is advisable to use the usual water-soluble and / or water-insoluble Stabilizers for the peroxy compounds together with them in amounts of 0.25 - 10% by weight to be incorporated4 As water-insoluble stabilizers, e.g. 1 - 8, preferably Make up 2 - 7% of the weight of the entire preparation, they are mostly suitable Precipitation of magnesium silicates obtained from aqueous solutions MgO: SiO2 = 4: 1 to 1: 4, preferably 2: 1 to 1: 2 and in particular 1: 1; Soluble as water Stabilizers, which can be present together with water-insoluble ones, are suitable differs from the above-mentioned complexing and precipitating agents for calcium ions those organic complexing agents that also have a pronounced complexing power for heavy metal ions, e.g.

the alkali salts of ethylenediaminetetraacetic acid, aminotrimethylene triphosphonic acid or 1-hydroxyethane-1,1-diphosphonic acid.

In order to wash at temperatures below 80 00, in particular to achieve a satisfactory blooming effect in the range of 60 - 40 ° C preferably activator-containing bleaching components are incorporated into the preparations.

Serve as activators for per-compounds that supply H2O2 in water certain N-acyl, O-acyl compounds that form organic peracids with this H2O2, in particular acetyl, propionyl or benzoyl compounds, as well as carbonic acid or Pyrocarbonic acid esters. Compounds that can be used include: N-diacylated and N, N'-tetraacylated amines such as N, N, N ', N'-tetraacetyl methylenediamine or ethylenediamine, N, N-diacetylaniline and N, N-diacetyl-p-toluidine or 1,3-diacylated Hydantoins, alkyl-N-sulfonyl-carbonamides, e.g. N-methyl-N-mesyl-acetamide, N-methyl-N-mesyl-benzamide, N-methyl-N-mesyl-p-nitrobenzamide, and N-methyl-N-mesyl-p-methoxybenzamide, N-acylated cyclic hydrazides, acylated triazoles or urazoles such as monoacetyl maleic hydrazide, O, N, N-trisubstituted hydroxylamines such as O-benzoyl-N, N-succinyl-hydroxylamine, O-acetyl-N, N-succinyl-hydroxylamine, O-p-methoxybenzoyl-N, N-succinyl-hydroxylamine, O-p-nitrobenzoyl-N, N-succinylhydroxylamine and O, N, N-triacetyl-hydroxylamine, N, N'-diacyl-sulfurylamide, such as N, N'-dimethyl-N, N'-diacetyl-sulfurylamide, and N, N'-diethyl-N, N'-dipropionyl-sulfurylamide, Triacyl cyanurates, e.g. triacetyl or tribenzoyl cyanurate, carboxylic acid anhydrides, e.g. benzoic anhydride, m-chlorobenzoic anhydride, phthalic anhydride, 4-chlorophthalic anhydride, Sugar esters such as glucose pentaacetate, 1,3-diacyl-4,5-diacyloxy-imidazolidine for example the compounds 1,3-diformyl-4,5-diacetoxyimidazolidine, 1,3-diacetyl-4,5-diacetoxyimidazolidine, 1,3-diacetyl-4,5-dipropionyloxy-imidazolidine, acylated glycolurils such as tetrapropionylglycoluril or diacetyl-dibenzoylglycoluril, diacylated 2,5-diketopiperazines, such as 1,4-diacetyl-2,5-diketopiperazine, 1,4-dipropionyl-2,5-diketopiperazine, 1,4-dipropionyl-3,6-dimethyl-2,5-diketopiperazine, Acetylation or benzoylation products of propylenediurea or 2,2-dimethylpropylenediurea (2,4,6,8-Tetraaza-bicyclo- (3,3,1) -nonane-3,7-dione or its 9,9-dimethyl derivative), Sodium salts of p- (ethoxycarbonyloxy) -benzoic acid and p- (propoxycarbonyloxy) -benzenesulfonic acid.

The active chlorine compounds used as bleaching agents can be more inorganic or be organic in nature.

The inorganic active chlorine compounds include alkali hypochlorites, in particular in the form of their mixed salts or addition compounds to orthophosphates or to condensed phosphates such as pyro- and polyphosphates or can be used on alkali silicates.

If the washing and washing additives contain monopersulphates and chlorides, active chlorine is thus formed in aqueous solution.

The organic active chlorine compounds are in particular the N-chlorine compounds in question, in which one or two chlorine atoms are bonded to a nitrogen atom, preferably wherein the third valence of the nitrogen atoms is attached to a negative group leads, in particular to a CO or SO2 group. These connections include Dichloro and trichlorocyanuric acid or their salts, chlorinated alkylguanides or Alkyl biguanides, chlorinated hydantoins, and chlorinated melamines.

Dirt carriers can also be used in the preparations according to the invention be included, which suspends the dirt detached from the fiber in the liquor hold and thus prevent graying. To this end, water-soluble colloids are used of an organic nature, such as, for example, the water-soluble salts of polymeric materials Carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acid sulfuric acid esters of cellulose or strength. Water-soluble polyamides containing acidic groups are also useful suitable for this purpose. Soluble starch preparations and others can also be used use as the above starch products, such as degraded starch, aldehyde starches etc. Polyvinylpyrrolidone can also be used.

The enzyme preparations to be used are usually a mixture of.

Enzymes with various effects, e.g. from proteases, carbohydrases, Esterases, lipases, oxidoreductases, catalases, per oxidases, ureases, isomerases, Lyases, transferases, De.smolasn or nucleases. Of particular interest are those from bacterial strains or fungi such as Bacillus subtilis or Streptomyces griseus obtained enzymes, in particular proteases or amylases; the opposite alkali, per compounds and anionic surfactants relatively stable and still at temperatures of up to 700 C. are effective.

Enzyme preparations are usually supplied by the manufacturers as aqueous solutions the active ingredients or as a powder, granules or as cold atomized products in the Trade brought. They often contain sodium sulfate, sodium chloride, Alkali ortho-, pyro- or polyphosphates, especially tripolyphosphate. Special ones Value is placed on dust-free preparations; they are obtained in a manner known per se by incorporating oily or pasty monionics or by using Granu] .icren with the help of melting salts containing water of crystallization in your own water of crystallization.

Enzymes can be worked specifically for a certain type of dirt are specific, for example proteases or amylases or lipases; preferred one uses combinations of enzymes with different effects, especially combinations from proteases and amylases.

The detergents can be used as optical brighteners for cotton in particular Derivatives of diaminostilbene disulfonic acid or

contain their all-calcium metal salts. For example, salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazin-6-yl-amino) -stilbene-2,2 are suitable '-disulfonic acid or similarly structured compounds that replace the morpholino group a diethanolamino group, a methylamino group or a 2-methoxyethylamino group wear. Brighteners of the 1,3-diaryl-2-pyrazoline type are used as brighteners for polyamide fibers in question, for example the compound 1- (p-sulfamoylphenyl) -3- (p-chlorophenyl) -2-pyrazoline and similarly structured compounds which, instead of the sulfamoyl group, e.g. the methoxycarbonyl, 2-methoxyethoxycarbonyl, the acetylamino or the vinylsulfonyl group wear. Usable polyamide brighteners are also the substituted aminocoumarins, e.g. 4-methyl-7-dimethylamino or 4-methyl-7-diethylaminocoumarin. Farther The compounds 1- (2-benzimidazolyl) -2- (1-hydroxyethyl-2-benzimidazolyl) -ethylene are used as polyamide brighteners and 1-ethyl-3-phenyl-7-di-sithylamino-carbostyril are useful. As a brightener for polyester and Polyamide fibers are the compounds 2,5-di- (2-benzoxaz-olyl) -thiophene, 2- (2-benzoxazolyl) -naphtho [2,3-b] -thiophene and 1,2-di- (5-methyl-2-benzoxazolyl) -ethylene are suitable. You can also use brighteners of the substituted 4,4'-distyryldiphenyl type be present; e.g. the connection ) I, 4'-bis (4-chloro-3-suifostyryl) -diphenyl, also mixtures of the above-mentioned brighteners can be used.

Agents according to the invention are of particular practical interest from pulverized to granular texture, according to all known in the art Processes can be established.

For example, the powdery aluminum silicates can be easily split Mix wise with the other components of the detergent, being aged or pasty Products such as

Nonionics to be sprayed onto the powder. Another manufacturing option consists in the incorporation of the powdery aluminum silicates into the other, al watery ones Mash present constituents of the agent, which then go through crystallization processes or by drying the water in the trz is converted into a powder. After this Heat drying, e.g. on rollers or in atomizing towers, can then be heat and Incorporate moisture-sensitive ingredients, such as bleach components and Activators for these, enzymes, antimicrobial substances, etc.

According to a particularly preferred method, powdery to granular, well-protected preparations can be obtained from the knowledge of their manufacture still moist crystalline aluminum silicates with rounded corners and edges at least mixed with some of the other ingredients of the preparation and this mixture converted into the pourable product by a process known per se. This Procedure allows the after the. Precipitation in the X-ray crystalline form with Finely divided aluminum silicates transferred to rounded corners and edges in damp. State direct, i.e.

without laborious isolation and drying, to solid, preferably pourable To process preparations. It is a particular advantage of the method that the Aluminum silicate particles their degree of distribution determined by the manufacturing conditions essentially retained while drying them in the meantime Bake larger structures together.

The aluminum silicates to be used in these preferred processes can essentially be processed in the following delivery conditions: a) still flowing suspension of the aluminum silicate in the mother liquor in which it is at the end of the production process, the mother liquor preferably does not contain dissolved aluminum compounds; b) aluminum silicate, of which the mother liquor was partially separated; c) after partial or complete washing out of the Mother liquor resulting, nocii flowable suspension of the aluminum silicate in water; d) aluminum silicate from which the wash water has been partially separated.

The delivery conditions described under b) and c) include before especially tough pastes, but also those that appear powdery.

Products containing still adhering water.

The mother kettle usually still contains excess caustic alkalis and / or alkali silicates, which are found in the further processing of the aluminum silicates can be converted into components of the detergents or cleaning agents to be manufactured, optionally after neutralization with acids or acid salts.

The latter can be of an inorganic nature, such as carbon dioxide, Bicarbonates, sulfuric acid, bisulfates, other mineral acids etc. But also organic ones For this purpose, acids such as fatty acids or anionic surfactants can be used in acid form. It is also not acidic, but thus alkaline saponification into anionic Substances that can be transferred to surfactants can be used, such as the SO3 sulfonation products of olefins and the sulfoydation or sulfochlorination products of alkanes. Further acids which can be used at this point are those in the preparations according to the invention used complexing agents or precipitants for calcium (structural substances).

Partial or complete separation of the mother liquor can be advantageous be if one uses either the mother liquor in the manufacture of the aluminum silicates wants to lead back, or if neutral to weakly alkaline reacting preparations should be produced.

The conversion of the moist aluminum silicates into the pourable ones Preparations is essentially possible according to two procedural principles: 1. The moist Mixture of the aluminum silicates with at least some of the remaining detergent ingredients is made pourable by drying.

2. The aluminum silicate in contact with water or mother liquor is mixed with substances that make the water hydrate and / or crystallize tie.

The first principle of the process can be achieved by hot atomizing or drying of the water-containing mixture transferred into practice on hot surfaces.

With the second principle of procedure there are several possibilities of realization. If one assumes that water-containing aluminum silicates are still free-flowing, then leave them alone these spray themselves on the moving solid components, what e.g. on moving Plates, rotating drums, shovels and fluidized beds happen can. If the aluminum silicates are moist, but no longer flowable, powdery appearing masses, it is often sufficient to mix them with the solid components of the preparation to be manufactured in order to obtain a granulated product.

In addition to surfactants, the washing or cleaning agents according to the invention can be used and / or builder substances also contain, for example, the following components: non-surfactant-like Foam stabilizers or inhibitors, fabric softeners, chemically acting bleaches as well as stabilizers and / or activators for these, dirt carriers, corrosion inhibitors, antimicrobial substances, enzyme, brighteners, dyes and fragrances, etc. Of these are some, e.g. per compounds, active chlorine compounds and some enzymes against Moisture and / or heat unstable, so that they are mostly dry and cold mixes pourable product. Also oily or pasty components, such as e.g.

nonionic surfactants, antimicrobial substances, etc. are widely used subsequently added to the finished pourable product.

f3example The first step is the production of the aluminum silicates to be used described, for which no protection is sought here.

In a vessel with a capacity of 15 l, the aluminate solution became lower Stir mixed with the silicate solution. It was stirred with a stirrer n'L1 dispersion disk at 3000 revolutions / min.

Both solutions were at room temperature. It formed under exothermic conditions Reaction as the primary precipitation product is an X-ray amorphous sodium aluminum silicate. After stirring for 10 minutes, the suspension of the precipitate was in a Crystallization tank transferred, where it is 6 hours at 90 ° C with stirring (250 Revolutions / min.) Remained for the purpose of crystallization.

After suctioning off the lye from the crystal pulp and washing with deionized Water until the washing water running off had a pH of approx. 10 became the Filter residue dried.

Instead of the dried aluminum silicates one used in some Cases for the production of detergents or cleaning agents, the suspension of the crystallization product or the crystal pulp.

The water contents were determined by heating the predried for one hour Products determined at 800 ° C. The washed to pH 10 and then dried Aluminum silicates were then ground in a ball mill. Dic grain size distribution was determined using a sedimentation balance.

All t values are percentages by weight.

The calcium binding capacity of the aluminum silicates was as follows Way determined: 1 l of an aqueous, 0.594 g CaCl2 (= 300 mg CaO / l = 30 ° dH) containing and the solution adjusted to a pH value of 10 with dilute Na0II is used with 1 g of aluminum silicate added (based on AS). Then the suspension is 15 min. vigorously stirred for a long time at a temperature of 22 O0 (+ 2 ° C). After filtering off of the aluminum silicate, the residual hardness x of the filtrate is determined. Calculated from this the calcium binding capacity for the aluminum silicate increases to (30 - x). 10 mg CaO / g AS.

If the calcium binding capacity is determined at higher temperatures, e.g. at 60 ° C, the values are consistently better than those at 2200. This fact shows The aluminum silicates compared to most of the previously used in detergents proposed soluble complexing agents and provides a represent particular technical progress.

Production conditions for the aluminum silicate R I: Precipitation: 7.63 kg of an aluminate solution of the composition 13.2% Na2O; 8.0% Al2O3; 78.8 z H2O; 2.37 kg of a sodium silicate solution with the composition 8.0% Na2O; 26.9% SiO2; 65.1% H2O; Make-up ratio in moles: 3.24 Na2O; 1.0 Al2O3; 1.78 SiO; 70.3 H2O; Crystallization: 6 hours at 90 ° C; Drying: 24 hours at 100 ° C; Composition of the dried Product: 0.99 Na2O. 1.00 Al2O3. 1.83 SiO2. 4.0 H2O; (= 20.9% H2O) crystal form: cubic with strongly rounded corners and edges; mean particle diameter (for the range 0.34µ): 5.4µ; Maximum of the particle size distribution curve: lies below of 3 µ; Calcium binding capacity; 172 mg CaO / g ai.

The particle size distribution was determined by sedimentation analysis in Water at 25 ° C determined with 1 g of substance per liter of water; pH of the suspension = 10.1; Stand height of the suspension = 20 cm.

The aluminum silicate R I is also identified by the at the end of the description pictured scanning electron micrograph (Fig. 1) characterized.

Production conditions for the aluminum silicate R II: Precipitation: 12.15 kg of an aluminate solution with the composition 14.5% Na2O; 5.4% Al2O3; 80.1% H2O; 2.87 kg of a sodium silicate solution with the composition 8.0% Na2O; 26.9% SiO2; 65.1% H2O; Make-up ratio in moles: 5.0 Na2O; 1.0 Al2O3; 2.0 SiO2; 100 H2O; Crystallization: 1 hour at 90 ° drying: hot atomization of a suspension of the washed product (pH 10) at 295 ° C; Solids content of the suspension 46%; Composition of the dried Product: 0.96 Na 2 O. ? Al. 1.96 SiO2. 4 H2O; Crystal form; cubic with strong rounded corners and edges; Water content 20.5%: mean particle diameter (for the range 0-30µ): 5.4µ; Maximum of the particle size distribution curve is below 3 t; Calcium binding capacity: 172 mg CaO / g AS.

Characterization of R II by scanning electron microscope photography (Fig. 2).

For comparison, FIG. 3 shows a photograph of a crystalline sodium aluminum silicate, which consists of cubic crystallites with pronounced corners and edges.

Production conditions for the potassium aluminum silicate R IIa: It was initially the sodium aluminum silicate R II was produced.

After suctioning off the mother liquor and washing the crystal mass with demineralized The filter residue was water up to a pII value of 10 in 6.1 l of a 25% strength KCl solution slurried. The suspension was briefly heated to 80-90 ° C .; then became cooled and filtered off again and washed.

Drying: 24 hours at 100 ° C; Composition of the dried Product: 0.35 Na2O. 0.66 K2O. 1.0 Al2O3. 1.96 SiO2. 4.3 H2O; (Water content 20.3 Calcium binding capacity: 175 mg CaO / g AS.

The aluminosilicates described below agree with one another the precipitation and crystallization conditions and the analytical composition of the end product largely corresponds to the dried products discussed above. For this reason, these aluminum silicates are labeled with a behind Serving letter-number combination set "f" (= moist) from the dried ones Different products. These aluminum silicates were either used together with the Mother liquor used directly for the production of detergents and cleaning agents, or the mother liquor was decanted or filtered off (Nutsche filter or peeler centrifuge) and the possibly washed out with deionized water, still moist aluminum silicate powder worked out.

Production conditions for the aluminum silicate suspension R I f1: Precipitation; 7.63 kg of an aluminate solution with the composition 13.2% Na2O; 8.0% Al 2 O 3; 78.8% H2O; 2.37 kg of a sodium silicate solution with the composition 8.0 t Na2O; 26.9 % SiO2; 65.1% H2O; Na2O excess: 0.7 kg = 7%; AS content: 1.6 kg = 16%; Calcium binding capacity: 172 mg CaO / g ai.

Production conditions for the aluminum silicate R I f2:.

Precipitation: as under R 1 f1 Further processing: after crystallization Sucking off the mother liquor, rewashing with 10 l of water, AS content; 1.5 kg = 55%; Calcium binding capacity: 172 mg CaO / g AS.

The washing and cleaning agents according to the invention are now described With a content of aluminum silicates with rounded corners and edges, as well as their Manufactured using the dried aluminosilicate powders described above or the aluminum silicate suspensions obtained as described above or the moist ones Aluminum silicate powder. The salt-like constituents mentioned in the examples the washing or. Cleaning agents - salty surfactants, other organic salts as well inorganic salts - exist as sodium salts unless specifically stated otherwise something else is determined. The names and abbreviations in the examples have the following meanings: ABS11: the salt of a straight-chain condensation Olefins r; tt benzene and sulfonation of the resulting alkylbenzene Alkylbenzenesulfonic acid with 10-15, essentially 11-13 carbon atoms in the alkyl chain; "Soap": one made from a hardened mixture of equal parts by weight soap made from tallow and rapeseed oil fatty acids; "OA + x ÄO" or "TA + x ÄO": the addition products of ethylene oxide (ÄO) with technical oleyl alcohol (OA) or of tallow fatty alcohol (TA) (JZ = 0.5), where the numbers for x are those of 1 mole of alcohol indicate the molar amount of ethylene oxide added; "Nonionic": the one under the Trade name "Pluronic L 61" available addition product of ethylene oxide on a Polypropylene glycol ether with a molecular weight of 1900, the proportion of the polypropylene glycol ether 90 wt .-% and the proportion of polyethylene glycol ether 10 wt .-% ausmach.

"HPK sulfonate": a fatty acid methyl ester made from hydrogenated P @@ Sulphoners with SO3 obtain sulphonate; "Perb @ @@ @che Pe @ @@@ ferries. Composition : H2 @. 3 H2O; "EDTA": the salt of ethylenediaminetetraacetic acid; "HEDP": the salt of 1-hydroxyethane-1,1-diphosphonic acid; "DMDP": the salt of dimethylaminomethane-diphosphonic acid; "CMC": the salt of carboxymethyl cellulose; "Liquid water glass": a 34.5% strength aqueous solution of sodium silicate with the composition Na2O. 3.35 SiO; "DCIC": the sodium salt of dicloroisocyanuric acid.

According to the invention with the aluminum silicates described above The washing effects achieved were determined by washing tests on test fabrics made from unfinished or easy-care (= crease-resistant) finished cottons or blended fabrics made of polyester and finished cotton with a test soiling of soot, iron oxide, Kaolin and sebum (test fabric manufactured by the Krefeld Laundry Research Institute) demonstrated.

The experiments were carried out with tap water of 16 ° dH, partly in a launderometer, partly carried out in a commercially available 4 kg drum washing machine (25 l washing liquor). In the launderometer, each vessel with 2 test rags of 2.1 g each and 2 not soiled Cloths of the same material from ebonfalls are loaded with 2.1 g each. The drum washing machine was carried out with 6 test rags, each 20 x 20 cm in size and 3.8 kg of unsoiled tissue load of the same type. The aluminum silicate concentrations of the treatment liquors refer to the amount of active ingredient (determined by dewatering for one hour at 800 ° C); this also applies to the use of suspensions or those that are still moist Powders of aluminum silicates.

The washing times given for the individual experiments are based for the duration of the treatment at the temperature mentioned, including the heating times. Cold tap water was used for rinsing. Washing in the launderometer followed rinsing four times with tap water for 50 seconds each; with those in one commercial washing machine tests carried out was the sequence of washing and rinses through the Automatic of the washing program determined, as it was intended for the respective washed textile material. After drying and Ironing the textiles was their reflectance value in a photoelectric photometer "Elrepho" from Zeiss under the filter 6 (maximum permeability at 461 nm) measured.

The test fabrics used in the tests were in the condition in which they were supplied an emission value of approx. 43.

Example 1 .: This example demonstrates the washing effect of the invention aluminum silicates to be used in the absence of other detergent ingredients.

Test conditions: washing in the launderometer, 30 minutes at 90 ° C .; unfinished cotton as test fabric; 10 g / l calcium-binding active substance; Liquor ratio: 1:12.

As calcium-binding active substance, those used according to the invention were used Aluminum silicates and, for comparison, sodium triphosphate are used. It was too washed with water without any further addition.

Active substance remission none (water value) 42.4 Na5P3O10 76.8 aluminum silicate R I 76.0 aluminum silicate R II 74.0 The test results show that the primary detergency of aluminum silicates with rounded corners and edges practically corresponds to deln of the triphosphate.

Example 2: This example gives the composition of a preparation on, which is obtained by mixing a dry aluminum silicate with sodium perborate and a water-soluble complexing agent or precipitant for calcium with a du.rch Detergent powder obtained by hot atomization was prepared.

45 parts by weight of aluminum silicate R I; 22 "sodium perborate; 4.2" Complexing agents or precipitants for calcium; 28.8 "detergent powder of the composition: 19.8% ABS; 7.0% TA + 14 EO; 9.8% soap; 12.0% Na2O. 3.3 SiO2; 5.8% magnesium silicate; 4.3% CMC; 32.0% sodium sulfate; Rest water.

The following complexing agents or precipitants for calcium were used: oxalic acid, tartaric acid, citric acid, O-carboxymethyl-tartronic acid, O-carboxymethyl-methyl-tartronic acid, Na5P3O10, alanine, glutamic acid, nitrilotriacetic acid, ethylenediamine-tetraacetic acid, N, N-dimethylamino-methanediphosphonic acid, polyacrylic acid, polyhydroxy-polycarboxylic acid (produced by copolymerization of acrolein and acrylic acid in the presence of 11202 and treatment of the polymer according to Canizzaro). It showed a striking Improvement of the washing success compared to a preparation that replaces one of these Substances only contained 4.2 t of sodium sulphate. example 3: Detergents of the following are suitable for use in commercial laundries Recipes 3a and 3b: component content in% for detergent 3a 3b ABS 1.4 1.4 OA + 10 AO 7.6 7.6 Na2C03 18.3 18.3 Na2SiO3 5.4 5.4 aluminum silicate R II 18.3 33.4 Na5P3O10 16.7 5.8 CMC 0.8 - 0.8 brightener, Na2S04 10.0 10.0 1120 21.5 17.3 The Na5P3O10 can be bim detergent 3a by a phosphorus-free organic complexing agent for calcium in detergent 3b by HEDP or DMDP or another, calcium complex binding phosphonate, with a phosphorus-free complexing agent for calcium or by a calcium precipitant that does not form complexes (e.g. oxalic acid, adipic acid or sebacic acid in the form of the water-soluble salts).

Example 4: One for washing heavily soiled work clothes A certain detergent has the following composition: 18.0% OA + 10 AO; 60.0 5 Na2CO3; 12.0% aluminum silicate R II; 5.5% O-carboxymethyl-tartronic acid (Na salt); 1.3 % CMC; 0.3% brightener; 2.9% H2O. The following are the recipes of some ' further, aluminum silicate-based laundry detergent.

Detergent wt .-% component in the detergent component after Example 5 6 7 8 HPK sulfonate 1.0 2.6 - 1.6 ABS 4.5 4.7 7.1 TA + 14 Ko 2.3 1.9 - 6.4 OA + 10 AO - - - 4.1 Soap 2.0 1.6 3.2 Aluminum silicate RI 45.0 47.3 48.1 49.3 Na5P3O10 5.0 6.3 8.0 7.2 EDTA 0.2 0.9 0.2 0.2 Na2O. 3.3 SiO2 6.5 3.7 2.6 3.4 perborate 25.1 26.3 22.3 22.1 magnesium silicate 1.5 2.0 1.2 1.2 CMC - 1.3 0.9 1.5 1.6 remainder (Sodium sulfate and water) Example 9.

Glass bowls, Porcelain plates and cups with attached or burnt remains of minced meat, Milk and starch pudding or with dried starch or oatmeal porridge or. were stained with grease pencil or dried-on tar residues, using the rinsed the following preparations. The hardness of the tap water used was by one base exchanger built into the machine lowered to 3 ° dH (= 30 pp; n CaO); the detergent concentration was 3 g / l.

Component% by weight Component in the preparation comparison Da 9b N 5 3 10 44.0 20.0 0.0 aluminum silicate R I 0.0 24.0 44.0 Na2SiO3 40.0 40.0 40.0 Na2SO4 10.0 - 3.0 0.0 DCXC, 2.0 - 2.0 2.0 Nonionic 1.0 1.0 1.0 Water 3.0 10.0 13.0 Es it was found that most of the soiling with the low phosphorus according to the invention or phosphorus-free agents 9a and 9b were at least as easily removable as with the phosphorus-containing comparative product according to the state of the art, stubborn, The dirt according to the invention was found to be partially burnt-in soiling Cleaner is even superior to the comparable product. When using non-softened Tap water (e.g. 16 ° dH = 160 ppm CaO), an increase in the cleaning agent concentration is recommended to 5 g / l. Boispicl 10: In 25 kg of the aluminum silicate suspension R @ I f1 were 0.7 kg ABS acid, 0.35 kg OA + 10 tio, 0.7 kg sodium triphosphate, 0.5 kg water glass Na2O. 3.3 SiO2, 0.1 kg CMC stirred in one after the other and then the Excess alkali converted into Na2CO3 by reaction with yasform at C ° 2. The resulting Aqueous detergent formulation gave a free-flowing hollow sphere powder after hot atomization the composition: 7.5% ABS; 3.5% OA + 10 EO; 7.0% Na5P3O10; 5.0% water glass; 1.0% CMC; 40.0% aluminum silicate R I (based on AS); 25.5% Na2CO3; Rest water.

The preparation produced by hot atomization can be modified by adding Convert from perborate in quantities of 15 - 35% into a bleaching detergent.

Example 11: For the preparation of a detergent of the composition: 3.5% soap; 7.0% TA + 10 EO; 3.0% TA + 5 EO; 15.0% aluminum silicate R I (based on on AS); 20.0% Na5P3O10; 28.0% perborate; 3.0 96 water glass; 1.8% CMC; 0.5% EDTA; 2.5% MgSiO3; 5.0% Na2CO3; 11.7% water was granulated into a mixture of the dry ones Ingredients with the exception of the soap and perborate in a mixer made by the company Lödige, Paderborn, Germany. This mixer consisted of a horizontal cylinder with Cooling jacket. The cylinder content was by rotating, ploughshare-like blades provided arms mixed. After filling in the dry recipe ingredients became a mixture of the moist aluminum silicate R I f2, the water glass, the Soap and the two nonionics mixed in, whereby granules were already formed. The slightly moist granulate removed from the mixer was used to discharge the Heat of hydration ventilated, whereby part of the introduced water evaporated and the end product was a free-flowing granulate. The perborate became after cooling of the granules mixed in.

If you want to further or completely eliminate the triphosphate, cs is expediently replaced by a mixture of 65% Na2CO3 and 35% citrate or 35% O-carboxymethyl tartrate.

Example 12: For the production of a detergent for household dishwashers the composition: 35.0% aluminum silicate R I (based on AS); 35.0% Na2SiO3; 1.0% DCIC; 10.0% nonionic; 5.0% water glass; 14.0% water was used in that Mixer as in Example 11. It was the aluminum silicate R I f1, about half of the powdery Na2SiO3 and the nonionic introduced. Sprayed on this powder mixture the water glass was opened and then the remaining Na2SiO3 and the »CIC were added. A stream of air was passed through the granulate obtained in the niche, causing a Part of the introduced water evaporated.

As Examples 10-12 show, the aluminum silicate can be used directly Process on free-flowing detergents or cleaning agents without removing it from the mother liquor isolated or, if you have the Mother liquor completely or partially separated off liat without having to be dried. This increases the effectiveness of the aluminum silicates in no way in the detergents or cleaning agents obtained according to the invention impaired.

Claims (33)

Claims 1. Process for washing and cleaning solid materials, in particular of textiles, with an aqueous liquor in which finely divided water-insoluble, capable of binding the hardness constituents of water and a calcium binding capacity of 100 - 200 mg Cao / g anhydrous active substance containing, optionally bound Water-containing, synthetically produced crystalline aluminum silicates of the composition 0.7 - 1.1 cat; 2 / nO. 1.0 A1203. 1.3-3.3 SiO2, in the lfat; one with your calcium ion exchangeable cation of valence n, preferably an alkaline cation and in particular the sodium cation, means, are suspended, characterized in that these Aluminum silicate crystals have rounded corners and shrouds. 2. The method according to claim 1, characterized in that the aluminum silicate crystallites with rounded ticks and edges at least 80% of particles a size of 8 - in particular from 6 - 0.01 μ exist and practically no particles larger than 30%. 3. The method according to claim 1 and 2, characterized in that the Aluminum silicates exist as sodium aluminum silicates. 4. The method according to claim 1-3, characterized in that the suspended aluminum silicates with rounded corners and edges crystalline reaction products represent how they come from an approach whose molar composition is preferred in the range 2.5 - 6, Kat2 / nO; 1.0 A1205; 0.5-5.0 SiO2; 6o - 200 H20, where Kat2 / n has the meaning given in claim 1 and in particular the sodium ion means obtained by crystallizing the precipitate. 5. The method according to claim 1-4, characterized in that the Application concentration of the aluminum silicates in the range of 0.2-10 g AS / 1, in particular 1 6 g AS / 1 lies. 6. Verification according to claim 1 - 5, characterized gekennzei.chnet that the Treatment liquors contain substances that complex calcium and / cder to felling ability. 7. Ancestors according to claim 1-6, characterized in that the Calcium complexing and / or precipitating substances dissolved in the treatment liquor are. 8. The method according to claim 6 and 7, characterized in that one as complexing agents or precipitants for calcium compounds of the condensed type Phosphates, as well as the type of the following organic traces or their salts are used: Polycarboxylic acids, hydroxycarboxylic acids, aminocarboxylic acids, carboxyalkyl ethers, polyanionic polymeric carboxylic acids and phosphonic acids. 9. The method according to claim 6-8, characterized in that one the complexing agents or the precipitating agents for calcium in concentrations of 0.05 - 2 g / l begins. 10. The process of doing the washing of textiles according to claims 1-9, characterized in that characterized in that the treatment liquor at least one more washing, bleaching or contains substance with a cleaning effect. 11. The method of tin washing textiles according to claim 10, characterized characterized in that the liquor contains surfactants in amounts up to 2.5 g / l. 12. A method for washing textiles according to claim 10 and 11, characterized characterized in that the liquor contains inorganic or organic builders Contains amounts up to 6 g / l, 13. A method for washing textiles according to claim 10-12, characterized in that the liquor per compounds in amounts up to Contains 0.4 g / l active oxygen and optionally stabilizers and / or activators for the per connections. 14. A method for washing textiles according to claim 10-12, characterized characterized in that the liquor contains active chlorine compounds in amounts that 0.4 g / l of active oxygen are equivalent. 15. A method for machine washing dishes according to claim 1 - 9, characterized in that the application concentration of the aluminum silicates is in the range of 0.5-3 g AS / 1. 16. The method according to claim 15, characterized in that the treatment liquor has a pH value in the range of 8-13. 17. The method according to claim 1-16, characterized by the presence of inorganic vuld / or organic phosphorus compounds in such amounts, that the phosphorus content of the treatment liquor is not 0.6 g / 1, preferably 0.3 g / 1 exceeds. 18. To carry out the method according to claim 1-17 certain Detergents, bleaches and cleaning agents with a content of substances that bind the hardness constituents of water are capable, characterized in that they are as finely divided substances capable of binding hardness in water ikatc according to claim 1-4, as well as at least one more wash, bleaching or cleansing compound. 19. Composition according to claim 18, characterized in that it is the aluminum silicates according to claims 1-4 in amounts of 5-95, preferably 10-60% by weight from the dried products containing bound water. 20. Means according to claim 18 and 19, characterized by a content of organic and / or inorganic phosphorus compounds in such amounts that the total P content of the agent does not exceed 6% by weight and preferably 3% by weight. 21. Textile detergent according to claim 18-20, characterized in that that their composition lies within the following formulation: 5 - 30% by weight anionic and / or nonionic and / or zwitterionic surfactants, 5-70% by weight of compounds according to claim 1 - 4 2 - 45 wt .-% complexing agent for calcium, 0 - 50 wt .-% for Complex formation of non-capable washing alkalis, O - 50 wt. - bleaching agents as well as other, There are usually fewer additives in laundry detergents. 22. Mittcl for machine washing of Gcsciilrr according to claim 18 - 20, characterized in that their composition in the context of the following recipe lies: 10-60% by weight alkali silicates and / or carbonates and / or hydroxides, 10 - 65% by weight of aluminum silicates according to claim 1 "0-40% by weight of other common constituents of machine dishwashing detergents. 23. Composition according to claim 22, characterized in that the alkali silicates and / or carbonates and / or hydroxides partly by inorganic phosphorus-containing Complexing agents are replaced. 24. Means according to claim 22 and 23, characterized in that it contain at least one of the following substances in the specified amounts: 1.0 - 10 wt .-% active chlorine or compounds containing active oxygen, 0.5-10 wt. Surfactants, in particular nonionic surfactants, 2.0-20% by weight sodium sulfate and / or Water. 25. A method for producing agents according to claims 18-24, characterized in that characterized in that the powdery compounds according to claims 1-4 with the other ingredients of the agent mixed. 26. A method for the production of agents according to claims 18-24, characterized in that the pulverulent compounds according to claim 1 - 4 in an aqueous mixture of the water and heat stable components of the agent incorporated, this dries in a manner known per se and optionally the dried one Product mixed with components of the product that are unstable to heat or moisture. 27. A method for the production of agents according to claims 18-212, characterized in that the aluminum silicates, which are still moist from their preparation, are used according to claim 1 - 4 with at least some of the remaining components of the preparation mixed; and this Getni.sch into a pourable one according to a method known per se Product transferred. 28. The method according to claim 27, characterized in that the Aluminum silicates according to claims 1-4 processed after removing the mother liquor. 29. The method according to claim 27, characterized in that the Aluminum silicates according to claims 1 - 4 together with the mother liquor on a pourable Product processed. 30. The method according to claim 28 and 29, characterized in that salt-like constituents of such agents by reacting the in the reaction product existing excess alkali generated with the appropriate acids. 31. The method according to claim 27, characterized in that the moist aluminum silicates according to claims 1 - 4 by mixing with substances, which are able to bind the water as hydrated and / or crystalline water into a transferred pourable product. 32. The method according to claim 27, characterized in that one is a as an aqueous slurry mixture of at least some of the others Components of the agent mixed aluminum silicates according to claims 1 - 4 Drying converted into a pourable product. 33. The method according to claim 2'1-52, characterized in that one d3t obtained pourable products with further, in particular moisture-proof and / or heat-unstable ingredients mixed. L e r s e i t e